Diazoamino compounds and their



Patented July 5, 1938 UNITED STATES PATENT OFFICE DIAZOAMINO COMPOUNDS AND THEIR MANUFACTURE No Drawing. Application August 16, 1934, Serial N0. 740,179

22 Claims. (Cl. 260-459) This invention relates to a new type of diazoamino compounds and to compositions of matter containing them. The diazoamino compounds of V the present invention are especially suitable for use in the art of dyeing textile fibers of any origin, for instance in the dyeing or printing of cellulose, either natural fibers or regenerated cellulose, cellulose esters or others, silk, wool, or hair fibers or fabrics. The diazoamino compounds of the present invention also are useful as germicides, bactericides, and insecticides.

The diazoamino compounds of the present invention may be represented by the general formula wherein Ar represents an aromatic radical, which may be further substituted; R1 represents a saturated aliphatic or cycloaliphatic group, R2 represents hydrogen, a saturated aliphatic or cycloaliphatic group, or an aromatic group, or R1 and R2 together represent a polymethylene chain, and the groups R1 and R2 are joined to the -N- of the formula by a carbon of the R1 and R2 except in the case where R2 represents H, and R1 is joined to the ester group of the formula by a carbon of the R1 group and R1 and R2 may contain as substituents alkyl, hydroxy, alkoxy, aryloxy, sulfo, sulfato groups, halogen or a polymethylene chain, and R2 may contain an ester group of the type shown joined to R1 in the formula;

Acyl represents the residue of sulfuric acid, phosphoric acid, or a polybasic acid of the benzene or aliphatic series; i. e., Acyl represents the radical formed by subtracting the acid OH groups from the organic or inorganic acid, thus from H2804 two OH groups are subtracted leaving S02 as the Acyl group corresponding to this acid and from phthalic acid CsH4(COOH)2 two OH groups are subtracted leaving C6H4(CO)2 as the Acyl group corresponding to this acid;

Me represents hydrogen or'a metal;

n2 represents a positive integer;

:0 represents the number of esterified hydroxyl groups of the acid; and

1 represents the number of unesterified hydroxyl groups of the acid.

It should be noted in connection with the above formula that one, two, or more amino-diazo groups, -N=NR1(R2)OAcyl(-OMe) may be joined to Ar; that is, the compounds may include not only diazo nuclei but tetrazo nuclei and so 011. Further, Ar may contain one or. more other substituents, e. g. halogen, nitro, alkyl, aryl, aralkyl, alkylaryl, alkoxy, aryloxy, azo, primary, secondary, or tertiary amino, sulfo, sulfite, hydroxy, and carboxy substituents.

The diazoamino compounds of especial importance and which constitute one of the preferred embodiments of my invention may be represented by the formula:

wherein, Ar has the value previously ascribed but is free from groups conferring solubility in water, sulfonate and carboxylate groups in particular; R1 represents a hydrocarbon group, R2 represents hydrogen or a hydrocarbon group, or R1 and R2 together represent a hydrocarbon group [i. e. hydrocarbon groups of the classes assigned in connection with Formula (1) l;

Acyl has the value previously ascribed but preferably represents S02;

Me represents hydrogen, sodium, or potassium.

The compounds of my invention are especially applicable to the dyeing of textile fibers and may be used for this purpose in a manner similar to diazo or nitrosamine compositions. The diazoamino compounds of this invention are stable in the presence of coupling components and hence may be used for the preparation of stable dye compositions comprising one or'more of the di azoamino compounds and a suitable coupling component or components.

Coupling of the diazoamino compounds of this invention with the coupling components normally employed with the corresponding diazo compounds may be eifected by treatment with acid, as by introducing an acid into the bath containing a solution of the diazoamino compound and the coupling component, or by subjecting fibers containing a coupling component to the action of an acidified bath of the diazoamino compound or by subjecting fibers impregnated with a solution or paste of the diazoamino compound and a coupling component to the action of an acid bath or acid vapors. In the case of the diazoamino .compound of the present invention coupling is much more energetic and more complete than with the diazoamino compounds formerly employed, and dyeings of greater depth and brilliance are therefore obtained. The reason for the improved results in these respects appears to lie in the fact that cleavage of the diazoamino linkage is accompanied by breakage of the link binding the organic residue R1 above to the polybasic acid radical. Thus one acid radical is set wherein Ar represents an aromatic radical as prefree and the action of this free acid radical materially promotes further cleavage of the diazoamino linkage. The cleavage is most complete in the case ofdiazoamino compounds formed'ioy the cgupling ef a diazo compound with the partial ester of a hydroxy organic primary or secondary amine and an inorganic polybasic acid o Ac 1 -oMe), of the class previously mentioned or a strong or- I: ganic polybasic acid. The double cleavage which i. takes place using the diazoamino compounds of wherein A; represents an aryl group, e. g. phenyl, this inventicen may be demonstrated by the folnaphthyl, diphenyl, anthranyl, anthraquinonyl, lowing equation; orgcarbazole, which may contain as substituents i one or more of the following: chlorine, bromine,

containing a coupling component or developer and a diazoamino compound of one of the follogging types: a i

and

CHz-CHg-CH; Ar-N=N2 r i i nitro, alkyl, aryl, aralkyl, alkylaryl, alkoxy, aryl- CHTCHHJE oxy, azo, amino, sulfo, hydroxy, and carboxy E OHzOl5([)rfi1g.SOaNa +HN (3) groups; R1 represents a hydrocarbon group, R2 2.

represents hydrogen or a hydrocarbon group, or R1 and Ratogether represent a hydrocarbon group [i. e. hydzocarbon groups of the classes assigned in connection with Formula (1) l; Me represents hydrogen or a metal, 1; represents a positive integer, preferably 1 or 2, and m or 112 represents a whole number, in particular l, 2, or 3. 5

The products of the present invention are suitable for the preparation of either water soluble or water insoluble azo dyes. They are especially suited for the production of azo dyes of the irisoluble type and the invention in its preferred aspects is directed to the diazoamine compounds or compositions derived from diaze compounds free from sulfonate or carhoxylate groups and, The diezoemihe Compounds of the yp p in the case of compositions containing a cou- Sehtedby Formula 6 may be P p y 0011- pling component, components free from such Fling anilromafie 1110110- poly-diazonium Sa groups, 1 with an 'amino partial ester. The coupling may The diaz 'oamino compounds of this invention, be represented y the following equation; especially those in which the amino ester group Ar(N=Nz) l-n [HIII-R b 1 comprises an OS OzOMe radical, wherein Me R2 represents H, Na, or K, possess notable solubility in water or aqueous alkaline solutions and hence I are especially valuable for" use where rapid and complete solution is desirable; this property constitutes a marked advanta'ge of the compounds of the present invention whether they are employed as etc.

The diazoamino compounds of the present in- "manner and may be represented by the following vention may be prepared by coupling anj aroi matic diaz'onium salt of the general formula: j (9) Ar-(N=; Tz)n (4) In either case is advantageous to add an alka- L line rea cut to bind the acid liberated duri 'iously set forth, represents an acid group, for V the wuiling. alkaline reagent may example represents positive integer added either during coupling or after as desired.

of to l Stoi t .1 uanfl; of or azoamino compound 1n the compositions of my C r7153 1 y p y invention may vary widely. Preferably, however, gfii ammo'partml Qster of l general I mix the two constituents in about stoichioi J, I metrical quantities. The compositions may I J Q' comprise the constituents in dry form or in solu- 1 tion. The dry composition may be prepared by wherein R1, R2, Acyl, Me, a: and 1 have the values; mechanical admixture of the two constituents previously ascribed in the discussion of Formula in solid phase or by evaporating a solution of the i and n2 represents a positive integer indicating two constituents. the number of primary or secondary amino While the present invention is of general apgroups joined to the organic rae' ical R1, preferplicability to the class of compounds indicated ably 1, 2, or 3. 7 above, especially those of Formulae (6) and (7),

The reaction to form the diazoamino com- I have found ithat the best results may be obpound proceeds at low temperatures. The coutained when the .diazoamino compounds are prepling of the diagonium salt with th ami parpared by the reaction of an aromatic diazoni'im tial ester is advantageously effected by bringing salt with a sulfuric acid partial ester of hytogethei" aqueous solutions of the individual I'G-E droxy ated aliphatic amines; either fi 'y "actantsin the presence of an alkaline; medium secondary. As previously indicated, such comiwhich serves to bind the acid liberated by the P 91 Which eontain'atleeiet One 02 Me coupling. The diazoamino compound may be reradical, p e pr p r r n rin h m escovered by crystallization, including salting out, pecially suitable for the pu poses of t invenor by drying the solution containing it in vacuum tion. When the esters are those of polyhydroxy or in other suitable manner, for instance with aliphatic amines, one or more of the hydroxy the aid of an inert gas or on a rotary drum drier. QPS ay be esterifiei The products P pe In its preferred aspects my invention compreas first indicated are diazoamino-aliphatic eul- 75 hends the preparation of dyestufi compositions furic acid partial esters, including b'pth the free represented by Formula 7 is effected in a similar V U 2,122,421 acids" and their meta s altspthe alkali-metal salts and particularly the sodium salts beingthe preferred form of these compounds for use inadmixture with the various known coupling components. 7

The compositions containing a diazoamino compound of the present invention and a coupling component, may, be applied to textile fibers in the usual manner. They are particularly suitable for the dyeing of fabrics by the printing process. A printing paste is prepai'edby mixing together about stoichiometrical quantities of a diazoamino compound of the type-previously defined and a coupling component, adding to the mixture sodium hydroxide solution in quantity sufficient todissolvethe components and making up the mixture to a. printing paste in the usual manner by adding thereto a thickening agent such as starch or gum tragacanth and the necessary quantity of water. .If desired, Turkey red oil or other assistants or solvents may beadded. The fabric is printed with this printing paste in the usual manner; then, either with or without drying and steaming it is treated for a short time, say around 20 seconds, in a bath containing an acid, for example 3% to 10% of formic acid, acetic acid, or oxalic acid at a temperature be tween 50 and 90 C. The bath may also contain other assistants, penetrants, etc., for example around 10% of Glaubers salt (Na2SO410I-I2O), or sodium chloride (NaCl), or sodium acetate (CH3COONa). Instead of developing the dye in an acid bath, it may be developed by passing it 1 through an acid vapor ager containing, for example, steam and vapors of acetic or formic acid or both. After development of the print in any of the above manners, it may be rinsed, washed,

and dried in the customary manner. 1

As mentioned earlier in this application, the

diazoamino compound of the present invention may be prepared from diazotized aromatic amines and primary or secondary amines containing a partial ester group. The partial ester group may be introduced into the amine by melting andrfusing together and/or by'condensing in appropriate solvents, and/or in the presence of catalysts, the free polybasic acids or their anhydrides or acid chlorides or mixtures thereof and an hydroxylated amine in its free state or in its combined N- salt, state. Since the esterification of hydroxy compound's is well known, the description of the preparation of the compounds and compositions of the present invention will be described in the examples commencing With theamino organic partial esters. The'invention is of a broad scope and the examples are inserted as a demonstration of its general applicability and not by way of limitation. Thus the invention may be applied to diazo compounds obtained by diazotization of the following aromatic amines:

' S-chlor-aniline,

4-chlor-2-arnino-1-methyl benzene, 4-chlor-2-amino-1-methoxy-benzene, 4-nitro-2-amino-l-methyl-benzene,

' 5-nitro- 2-amino-l-methyl benzene, 3-nitro4-amino-l-methyl-benzene, 5-chlor-2-amino-l-methyl-benzene, 3-chlor-2-amino-l-methylfbenzene, 6 -chlor-2-arnino-l-methyl-bnziane, 3-chlor-4-amino-l-methyl-benzene, 4,5-dichlor-2-amino-l-methyl-benzene, 2,5-dichlor-4-amino-l-methyl-benzene,

, G-benzoylamino 4- chlor-3-amino-1-methoxybenzene,

I 2,5 dichlor-l-amino-benzene,

l-amino-anthraquinone, 1-amino-4-benzoylamino-anthraquinone, anilini-sulfonic acid, 2,5 -dichlor-anilinel-sulfonic acid, 2-amino-diphenyl-sulfone,

2-amino-4'-methyl diphenyl sulfone-4-su1- fonicacid,

2-amino-4-hydroxy diphenyl-sulfone-3'-carboxy-l-sulfonic acid,

-2-amino-5-chlor-l-benzoic acid methyl ester,

2-amino-4-methyl-5nitro-benzoic acid, 1-amino-anthraquinone-2-sulfonic acid, 2-amino-l-carboxy-benzene-4-sulfonic acid, 2-amino-4-methoxy -5- phenylamino-l-chlorobenzene,

4,6- dichloro-2-amino-l-methyl-benzene,

ZA-dimethyl-aniline, 3-amino-4-methoxy -6- nitro -lmethyl benzene,

3-amino-4-methoxy-6-benzoylamino-1-methy1 benzene,

3-benzoy1amino-4,6-dimethoxy-aniline,

4,4'-cliamino-3,3-dimethoxy-azobenzene, 2,6-dimethoxy-4-benzoylamino-aniline, 2,5-dimethoxy-4-benzoylamino-aniline, 2-methoxy-4-benzoylamino-5-ethoxy-aniline, 4-nitro-4-amino-2,5'-dimethoxy-azobenzene, 3-nitro-4-amino-2',5-dimethoxy-azobenzene, 4-methyl-4'-amino -2- methoxy-S-methyl-azobenzene,

4-chloro-4'-amino-2',5-diethoxy-azobenzene.

The following partial esters illustrate the wide variety of compounds which may be coupled with diazo compounds to produce the diazoamino compounds of the present invention:

met-hyl-amino-butyl-sulfuric acid, ethyl-amino-butyl-sulfuric acid, hydroxy-ethyl-amino-ethyl-sulfuric acid, amino-diethyl-disulfuric acid, cyclohexylamino-ethyl sulfuric acid, lfi- (beta-ethyl-hexyl) -amino-ethyl s u l i u r i c aci N-(beta ethyl-cyclohexyl) -amino ethyl sulfuric acid,

hydroxy-ethyl-amino-ethyl-phthalic acid, the sulfonic ester from ethanolamine and 4- sulfo-benzoic acid,

methyl-amino-ethyl-dichlor-phthalic acid, sulfo-ethyl-amino butyl-sulfuric acid, the mono (methylamino-ethyl-ester) of benzene-p-disulfonic acid,

the disulfonic ester from dipropanol amine and l-sulfo-benzoic acid,

mono- (methyl-amino-ethyl) -maleic acid ester, N-n-butyl-amino-ethyl-sulfuric acid, isohexylamine-beta-sulfuric acid, tetrahydro-naphthylamine-ethyl-su1furic acid, the disulfonic ester from diethanolamine and 3- sulfo-benzoic acid,

piperidine-beta-sulfuric acid, cyclo-hexyl-amine-B-sulfuric acid, pyrrolidine-alpha-methyl-sulfuric acid,

the sulfonic ester from methyl-ethanolamine and i-sulfo-benzoic acid, 1

methylamino-ethyl-acid-succinate, methylamino-ethyl-acid-chlor-maleate, ethylamino-ethyl-phthalic acid, methylamino-propyl-sulfuric acid, methyl-amino-ethyl-phosphoric acid ester, 2,5-dichloro-phenyl-amino-butyl-sulfuric acid, 4-methoxy-phenyl-amino-ethyl-sulfuric acid, flmethoxy phenyl amino diethyl sulfuric aci 3 chloro tolyl-amino butyl-sulfuric acid,

' tate, and about 1000 parts of water.

pling with diazo compounds may be employed with the diazoamino compounds of the present invention, for instance the naphthols and naphv tholates, 2,3-hydroxy naphthoic acid arylides, alkyl phenyl-pyrazolones, aceto-acetic acid arylides, 2-hydroxy-carbazole-o-carbonic arylides, and the ZA-dihydroxy-quinolines. Specific examples of these coupling components are given in connection with the following examples and in the table of dyestuif compositions which is a part hereof.

The following examples will serve to further illustrate the present invention.

Example 1.l parts by weight of 3-chloraniline are diazotized in the customary manner by means of hydrochloric acid and sodium nitrite to yield an aqueous solution of 3-chlorphenyl-diazonium chloride. This solution is gradually run into an aqueous solution of the sodium salt of N-methyl-amino-butyl-sulfuric acid. The ester solution comprises about 150 parts of the ester, about 400 parts of sodium ace- During the addition of the diazonium chloride, the aqueous ester solution is stirred and cooled so as to maintain the temperature at 0 to C. The diazonium chloride addition is regulated to avoid any substantial rise in temperature. After the addition of the diazonium chloride is completed, the solution is made alkaline with soda ash in slight excess and agitated at 0 C. for from one to two hours or until nofree diazonium chloride can be detected. The diazoamino ester salt which forms has the following formula:

The diazoamino sodium sulfate is then salted out from the solution by adding thereto 200 parts of sodium chloride. The crystallized ester is separated by filtration or centrifuging and is dried.

The product is a yellow powder readily soluble in are diazotized and the diazonium salt solution is added to an aqueous solution of methylaminobutyl-sodium-sulfate containing about 150 parts of the partial ester salt. The product may be recovered from solution in the same manner as in Example 1 or the aqueous solutionmay be evaporated to dryness in a Vacuum or on a double drum drier under reduced pressure. The product is a yellow powder readily soluble in water, having the probable formula:

In a similar manner diazoamino compounds may be prepared from the other chlorand nitrosubstituted anilines previously mentioned and methylamino-butyl-sulfuric acid or alkali-metal salts thereof; The products thus formed are yellow to orange powders, readily soluble in water. They are stable towards alkalis but are decomposed into the corresponding diazonium salts, methylamino-butanol, and sulfuric acid by the action of acid reagents thereon.

Example 3.'10 parts by weight of sulfanilic acid (NI-I2C6H4pSO3I-I-I-I2O) are diazotized in the usual manner with sodium nitrite and hydrochloric acid, and the resultant solution of the diazonium chloride is introduced into an aqueous solution of N-(beta-ethyl-cyclo-hexyl) -aminoethyl-sulfuric acid, the solution comprising about 14 parts of the partial ester, 30 parts of sodium acetate, and 200 parts of water. The cooling, stirring, and addition of the diazonium chloride are regulated as in Example 1 so that the temperature does not exceed plus- 5 C. The solution is then rendered slightly alkaline by addition of sodium carbonate. The diazoamino compound which forms is salted out by the addition of sodium chloride to the cold liquid, is filtered off and dried at a low temperature. The dry product is a yellowish powder very soluble in water. It may be represented by the following structural formula:

CH CH,

In a similar manner diazoamino compounds sulfo-substituted anilines previously mentioned. Water-soluble azo dyestuffs may be prepared from any of the resultant diazoamino compounds by dissolving the diazoamino compound in water and adding thereto a coupling component in aqueous solution and thereafter acidifying the solution with a strong organic acid, for example formic acid, acetic acid, or oxalic acid until an acid solution of 3% to strength is obtained. Preferably a small amountof sodium acetate is added prior to acidification. The formation of the azo dye can be accelerated by the application of heat and proceeds rapidly at a temperature of from 50 to 60 C. The coupling can be effected even more rapidly by using a mineral acid for acidification, for example hydrochloric acid, or an acid salt such as sodium bisulfate. The preparation of soluble azo dyestuffs of the above type also may be effected by introducing an aqueous solution of a coupling component into an aqueous solution of the diazoamino compound to which an acid previously has been added.

Example 4.386 parts of the diazoamino compound obtained from 2-nitro-4 methyl-phenylmay be prepared from any of the carboxyor diazonium chloride and .methylaminobutyl-sodiumr-sulfate and having the probable formula:

are dissolved in an aqueous solution comprising 1500 parts of water and about 100parts of sodium acetate. To the resultant solution an aqueous alkaline solution comprising 220 parts of acetoacetanilide, 2000 partsof water, and 45 parts of separates. This product maybe filtered off,

washed and dried in any suitable manner.

Example 5.An aqueous solution of the diazoamino compound formed by coupling 2-,nitro- 4-methoxy-phenyl-diazonium chloride and cyclohexyl-amino-ethyl sulfuric acid, of the formula:

0211 -0 scion is treated with an alkaline aqueous aceto-acetic acid-2-toluidide solution containing an equimolar quantity of the aceto-acetic-toluidide, in the manner set forth in Example 1. {in orange yellow azo dye of the probable formula:

'7 QOCH:

CH N=N( JH 17 OzN amin o-diethyl-disodium-disulfate, and having the probable formula:

there is added 20 parts of acetic acid,- parts of alum, and 5 parts of sodium acetate.

Cotton fabric is impregnated in the customary manner .with. 2-hydroxy-3-naphthoic acid-2'- naphthylamide; for instance 50 grams of cotton may be impregnated with a liquor containing to 5ngrams of the amide, about 1 to about cc. of 34 B. (28%) NaOH and about 1 to about 10 cc. of Turkey red oil of 50% strength.

The impregnated cotton is introduced into the bath containing the acidified diazoamino compound and the bath is slowly heated to about 50 to 60 C. The formation of the azo dyestuif on the fiber occurs very readily. It has the probable formula:

CH3 OH O When the diazo compound can no longer be detected in the bath, the cotton is removed therefrom, -is rinsed, soaped at boiling temperature, rinsed again, and dried. A brilliant red of excellent fastness is thus obtained.

Example 7.The sodium salt of the diazoamino compound obtainable from 2-methoxy-5-chlorphenyl-diazonium chloride and N-methyl-aminobutyl-sulfuric acid and having the probable formula 1 in aqueous solution, is mixed in equimolar ratio with 2-hydroxy-3-naphthoic-acid-2anisidide in an aqueous solution containing an equimolecular quantity of NaOH.- The mixture is evaporated to dryness at a low temperature in vacuum.

70 parts by weight of the dry product are made up to 1000 parts with 50 parts Turkey red oil, 50 parts urea, 600 parts starch-tragacanth thickener, and the remainder water. The resultant printing paste may be printed on a textile fabric in the usual manner. The printed fabric is passed through an acid vapor ager at a temperature of 100 to 102 C., the ager being supplied with steam containing between say .05% and 1% of acetic and .05% and /2% of formic acid vapors to form the azo dye having the probable formula:

OCH:

N=N I (21) OOHs.

After a short period of contact of the printed fabric with the acid vapors in the ager, say 2'- Ex mple 9.--About 3 parts of the diaaoamino compound from 3-chlor-phenyl-diazonium-chloride and ethylaminobutyl sodium sulfate r N=NN i (OH2)4OSQ2ONa V and about 2% parts of Z-hydroxy-3-naphthoic 1O acid-2-toluidide were made up to a paste with hot water with the addition of 3 parts of the mono-ethyl ether of glycol. To this paste 3 parts by weight of 36 B. NaOH (30%), 60 parts by e weight of neutral starch tragacanth thickener are added, and the product is made up to 100 parts by weight with water. is applied to cotton fabric in the' usual manner. The print is then steamed for around 5 minutes v (or as an alternative is hung in contact with the atmosphere for about 21 hours). The cotton is then introduced for a short time into an aqueous bath maintained at about'80 to 90 C. and containing 50 grams acetic acid and 50 grams sodium sulfate per liter. By thistreatm of the probable formula: 5

is developed on'the fiber yieldin This printing paste ent the azo dye g a print of a very brilliant orange shade of excellent fastness. 35 ,A similar result is obtained by developing the print in an acid bath containing formic acid, 0;;- "alic acid, or another strong organic acid instead 'of the acetic acid mixture. Likewise development a vapor ager cantaining a volatile acid 40 7, such as acetic acid produces similar results.

' It will be obvious from the above examples that 'the procedure involved in the preparation and use of my new diazoamino compounds or compo- Any of the usualmethods of developing azo dyestuffs by coupling diazoamino compounds and coupling components may be employed with the diazoamino compounds of the present invention.

Diazoamino compounds from diacid esters of A1N=NN R50SO2OM) 2 wherein Ar represents an aromatic radical, R5

dialkylolamines and cycloalkyldiol amines as well as those from esters of 'mono-alkylolamines and cycloalkyl mon-olamines constitute an important group among the products of the present invention. The di-ester diazoamino compounds of greater importance may be represented general formula by the represents an' alkyl preferably with 4 carbon or Na;

' The following table further illustrates the nature of compositions of dyes that may be obtained bythe application of invention. In this table are shown the shades of dyeings obtainable with the diazoamino compounds and the coupling componentsset forth. It will be understood that such dyeings may be obtained by substantive preparation, or by printing a textile fiber witli' a printing paste'containing the diazoamino compound and coupling componenteand subsequently developing, or by impregnating the textile fiber with one of the components and subsequently'developing the'dye by bringing the im- V pregnated fiber into contact with the other com- 7 45 sitions is capable of almost lirnitless variation. ponent under conditions favoring azo coupling.

No. Base Stabilizer 1 FOI'IIliIJa 7 Coupling component Shade 1 2.5- dichloro -"l Hydroxy ethyl amino QHr-CHz-OH Diacetoacetyl o toli- Yellow.

aminobenzene. ethyl sulfuric acid. dide.

s 7 r J j s CHr-OHrOSOzH v 2 2.5 dichloro Q l Hydroxy ethyl amino OHr-QHr-OH 2.5 dichloro 4 nitro- Do. v aminobenzene. ethyl phthalic acid. 7 l-aceto-acetylamino- 1' 7 EN i benzene.

s 7 s p V CHz CHzOOO--i@aH4'COQH 3 4- chloro-2-amino- Sulfonic ester from "CH3 Diacetoacetyl-o-toli Do.

1-1nethylbenmethyl ethanoladide ;zene. mine and 4-sulfo EN benzoic acid. V

V I CHrCHrO-SOT 4 4.5 dichloro 2- Sulf onic ester 'from: -.do Do.

amino-l-methm c is hylethanolaylbenzene. mine and 4-sulfon benzoic acid. a gi-chloro-Z-azhino- Methyl-amino-ethyl- CH3 e a be.

1 methoxy dichlorphthalic acid. f GOOH I benzene. HN\

OH2''CH20O0C1 V V Q 01 6 2.5-dichloro -1 N gethane sulfonic onronrsoan' l p methyl-4-am1- amino-butyl sulfuric r do Do.

acid. HN e nobenzene.

N Base Stabilizer Formula Coupling component Shade 44 6-amino-3-ben- Ethyl-amino-butyl- C211 Sodium compound of Do.

zoylamino-lA- phosphoric acid. 2-hydroxy-naphthadimethoxyben- EN 0 OH lene-3-carboxylic zene. acid O-toluidide.

45 4-chloro-2-amino- Methyl-aminopropyl- Sodium compound of Brown.

l-methylbensulfuric acid ester. Z-hydroxy-carbazene. zole o carboxylic acid 2-toluidide.

46 i-nitro 4 ami Acid ester from meth- Sodium compound of Black.

no-25-din1ethyl ethanol amine 2-hydroxy-naphtha oxyazo ben and benzene-disullene-3-carboxylic zene. ionic acid. acid o-toluidide.

47 3-nitro-4-ami- Hydroxy-ethyl-amino- Sodium compound of Do.

no-25-dimethethyl-sulfuric acid. 2-hydroxy-naphthaoxyazo ben lene-3-carboxylic zene, acid alpha-naphthylamide.

48 4-methyl-4-ami- N-ethane-sulfonic Sodium compound of Do.

no-Z-methoxyamino-butyl-sulfu- 2-hydroxy-naphtha- 5-methylazoric acid. lene-3-carboxy1io benzene. acid o-toluidide.

49 4-chlor0-4-ami- Hydroxy-ethyl-amino- Sodium compound of Do.

no 2'5 diebutyl-sulfuric acid. 2-hydroxy-naphthathoxy-azo-benlene-3carboxylic zene. acid alpha-naphthylamide.

I claim: 4. As a new compound a diazoamino ester of 1. As a new compound a diazoamino ester of the following general formula wherein Ar .represents an aromatic radical, R1 represents a. saturated aliphatic or cycloaliphatic group, R2 represents hydrogen, a saturated aliphatic or cycyloaliphatic group, or an aromatic group, or R1 and R2 together represent a polymethylene chain forming a heterocyclic ring with the N,Acyl representsthe residue of sulphuric acid, phosphoric acid, or a polybasic acid of the benzene or aliphatic series, Me represents hydrogen or a metal, 712 represents a positive integer, and x and 1 each represents a positive integer.

2. As a new compound a diazoamino ester of the following general formula wherein Ar represents an aromatic radical, R1 represents a saturated aliphatic or cycloaliphatic group, R2 represents hydrogen, a saturated aliphatic or cyclo-aliphatic group, or an aromatic group, or R1 and R2 together represent a polymethylene chain forming a heterocyclic ring with the --N-,Merepresents hydrogen or amonovalent metal, Acyl represents the residue of sulfuric acid, phosphoric acid, or a polybasic acid of the benzene 'or aliphatic series, 1/ represents a positive integer, and n1 represents an integer less than 4.

3. As a new compound a diazoamino ester of the following general formula wherein Ar represents an aromatic radical, R1 represents a saturated aliphatic or cycloaliphatic group,R2 represents hydrogen, a saturated aliphatic or cycloaliphatic group, or an aromatic group, or R1 and R2 together represent a polymethylene chain forming a heterocyclic ring with the N--, Me represents hydrogen or a monovalent metal, Acyl represents the residue of sulfuric acid, phosphoric acid, or a polybasic acid of the benzene or aliphatic series, 1 represents a positive integer, and 122 represents an integer less than 4.

the following general formula wherein Ar represents an aromatic radical, R1 represents a saturated aliphatic or cycloaliphatic group, R2 represents hydrogen, a saturated aliphatic or cycloaliphatic group, or an aromatic group, or R1 and R2 together represent a polymethylene chain forming a heterocyclic ring with the N-, Me represents hydrogen or a monovalent metal, Acyl represents the residue of sulfuric acid, phosphoric acid, or a polybasic acid of the benzene or aliphatic series, and a: and 1/ represent positive integers.

5. As a new compound a diazoamino ester of the following general formula wherein Ar represents an aromatic radical free from sulfonate and carboxylate groups, R1 represents a saturated aliphatic or cycloaliphatic group, R2 represents hydrogen, a saturated aliphatic or cycloaliphatic group, or an aromatic group, or R1 and R2 together represent a polymethylene chain forming a heterocyclic ring with the -N, Me represents hydrogen or a monovalent metal, Acyl represents the residue of sulfuric acid, phosphoric acid, or a polybasic acid of the benzene or aliphatic series, and 1/ represents a positive integer.

6. As a new compound a diazoamino ester of the following general formula ArN= N-N(R1OAcylOMe) 2 wherein Ar represents an aromatic radical, R1 represents a saturated aliphatic or cycloaliphatic group, and Me represents hydrogen or a monovalent metal.

7. As a new compound, an aromatic diazoamino-aliphatic sulfuric acid partial ester.

8. As a new compound a diazoamino ester of the following general formula I Ar N=NI|\ -R1O-SO20Me] I R2 'Il wherein Ar represents an aromatic radical free or a monovalent metal.

from sulfonate and carboxylate groups, Rrreprerepresents an acid group, and n1' 'represents an sents asaturatedaliphatic or cycioaliphatic hydrocarbon group, R2 represents hydrogen, a saturated aliphatic or cycloaliphatic group, or an aromatic group, Me represents hydrogen or a monovalent metal, and m represents an integer less than 4.

9. As a new compound a diazoamino ester of the following general formula f, Ar-N=NN R1-OSO2-OMe wherein Ar represents an aromatic radical, R1 represents a saturated aliphatic or cycloaliphatic hydrocarbon group, R2 represents hydrogen, a saturated aliphatic or cycloaliphatic group, or an aromatic group, Me represents hydrogen or a monovalent metal, and 112 represents an integer less than 4. 1

10. As a new compound a diazoamino ester of the following general formula wherein Ar rep-resents an aromatic radical free from siilfonate and carboxylate groups, R1 represents a saturated aliphatic or cycloaliphatic hydrocarbon group, R2 represents hydrogen, a saturated aliphatic or cycloaliphatic group, or an aromatic group, andMe represents hydrogen 11. As a new compound a diazoamino ester of the following general formula 7 wherein Ar represents an aromatic radical, R1 represents a saturated aliphatic or cycloaliphatic hydrocarbon group, and Me represents hydrogen or a monovalent metal,

12. As a new compound, an aromatic diazoamino-aliphatic sulfuric acid partial ester in the form of an alkali-metal salt.

13. As a new compound an aromatic diazoaminobutyl sulfuric acid partial ester in the form of a sodium salt. I e

14. As a new compound an aromatic diazoamin0-di(butyl sulphuric acid) partial ester.

15. The method of producing a diazoamino compound of the type set forth in claim 1, which comprises coupling a; diazonium salt of the general formula Ar-(N Nz) 11 wherein Ar represents an aromatic radical, 2 represents an acid group and n1 represents a positive integer, with an amino partial ester of the general formula HN R1-O ge 1 oMe wherein R1 represeiits a saturated aliphatic or cycloaliphatic group, R2 represents hydrogen, a saturated aliphatic or cycloaliphatic group, or angaromatic group, or R1 and R2 together represent a polymethylene chain forming a heterocyclic ring with the N, Acyl represents the residue of sulfuric acid,- phosphoric acid, or a polybasic acid of the benzene or aliphatic series, Me represents hydrogen or':a metal, n2 represents a positive integer, and :1: and g each represents a positive integer.

16. The method of producing a diazoamino compound of the typeset forth in claim 2, which comprises coupling in an alkaline medium an aromatic diazonium salt of the general formula Ar(N=N--z)n wherein Ar represents an aromatic radical, 2

integer less than 4, with an amino partial ester of the general formula H N-R1O-Acyl(-O'Me),,

I! 2i wherein R1 represents a saturated aliphatic or cycloaliphatic group, R2 represents hydrogen, a saturated aliphatic or cycloaliphatic group, or an aromatic group, or R1 and R2 together represent a polymethylene': chain forming a heterocyclic ring with the N, Acyl represents the residue of suifuric acid, phosphoric acid, or a polybasic acid'of the benzene or aliphatic series, Me represents hydrogen or a monovalent metal, and 1;: represents a positive integer.

17. The method of producing a diazoamino compound of the type set forth in claim 3, which comprises coupling in an alkaline medium an aromatic diazonium salt of the general formula wherein Ar represents an aromatic radical and 2 represents an acid group, With an amino partial ester of the general formula RN R1o-Ae 1 -0Me 2 1 2 j, 1 wherein R1 rep-resents asaturated aliphatic. or cycloaliphatic group, R2 represents hydrogen, a saturated aliphatic ;or cycloaliphatic group, or an aromaticngroup, or R1 and R2 together represent a'polyinethylene chain forming a heterocyclic ring with the N, Acyl represents'athe residue of sulfuric acid, phosphoric acid, or a polybasic acid of the benzene or aliphatic series, Me represents hydrogen or a monovalent metal, 1; represents a positive integer, and 112 an integer less than 4.

18. The method ;;of producing a diazoamino compound of the type set forth in claim 4, which comprises coupling in an alkaline solution a diazonium salt of the general formula ArN=Nz wherein Ar represents an aromatic radical and 2 represents an acid group, with an amino partial ester of the general formula wherein 94* represents an aromatic radical, R1 represents a saturated aliphatic or cycloaliphatic group, R2 represents hydrogen, a saturated aliphatic or c ycloaliphatic group, or an aromatic group, or R1 and R2 together represent a polymethylene chain forming heterocyclic ring with the N-, Me represents hydrogen or a monovalent metal, Acyl represents the residue of sulfuric acid, phosphoric acid, or a polybasic acid of the benzene or aliphatic series, and a: and y represent positive integers.

19. The method of producing a diazoamino compound of the type set forth in claim 5, which comprises coupling a diazonium salt of the general formula wherein Ar represents an aromatic radical free from sulionate and carboxylate groups and 2 represents acid group, with an amino ester of the general formula Hl| l'R OAcyl(0Me) wherein R1 represents a saturated aliphatic or cycloaliphatic group, R2 represents hydrogen, a saturated aliphatic or cycloaliphatic group, or

an aromatic group, or R1 and R2 together represent a polymethylene chain forming a heterocyclic ring with the N, Me represents hydrogen or a monovalent metal, Acyl represents the residue of sulfuric acid, phosphoric acid, or a polybasic acid of the benzene or aliphatic series, and 1 represents a positive integer.

20. The method of producing a diazoamino compound of the type set forth in claim 8, which comprisescoupling in an alkaline medium an aromatic diazonium salt of the general formula wherein Ar represents an aromatic radical free from sulfonate and carboxylate groups, 2: represents an acid group, and n1 represents an integer less than 4:, with an amino partial ester of the general formula wherein R1 represents a saturated aliphatic or cycloaliphatic hydrocarbon group, R2 represents hydrogen, a saturated aliphatic or cycloaliphatic group, or an aromatic group, and Me represents hydrogen or a monovalent metal.

21. The method of producing a diazoamino compound of the type set forth in claim 9, which comprises coupling in an alkaline medium an aromatic diazom'um salt of the general formula wherein Ar represents an aromatic radical and 2 represents an acid group, with an amino partial ester of the general formula wherein R1 represents a saturated aliphatic or cycloaliphatic hydrocarbon group, R2 represents hydrogen, a saturated aliphatic or cycloaliphatic group, or an aromatic group, Me represents hydrogen or a monovalent metal, and n2 represents an integer less than 4.

22. The method of producing a diazoamino compound of the type set forth in claim 10, which comprises coupling in an alkaline medium a diazonium salt of the general formula wherein Ar represents an aromatic radical free from sulfonate and carboxylate groups and 2 represents an acid group, with an amino partial ester of the general formula wherein R1 represents a saturated aliphatic or cycloaliphatic hydrocarbon group, R2 represents hydrogen, a saturated aliphatic or cycloaliphatic group, or an aromatic group, and Me represents hydrogen or a monovalent metal.

JEAN G. KERN. 

